Inhibition of acid-fading on dyed cellulose acetate with n:n&#39; diphenylethylene diamine



/ (1151-11121) STAT Patented at. 25,1941

INHIBITION. OF ACID-moms N DYED CELLULOSE ACETATE wrrn N:N' n1- PHENYLETHYLENEIDIAMINE Benjamin Collie, Charles Hugh Giles, and Donald Graham Wilkinson, Blackley, Manchester, England, assignors to Imperial Chemical Industries Limited, a corporation of Great Britain No Drawing. Application June 25, 1943, Serial No. 492,308. In Great Britain July is, 1942 4 Claims. 1 I

The present invention relates to a process for:

treating materials consisting of or containing cellulose esters or ethers in order to enhance the fastness of the colourations on the aforesaid materials when they are dyed 'or otherwise coloured by the application of dyestufls thereto.

It is known that materials consisting of or containing cellulose esters or ethers which have been coloured by dyeing or printing tend to fade when exposed to the action of the products'of.

combustion of coal gas, that is to say, when they are kept in an atmosphere which is contaminated acetate artificial silk cloth, which are worst discoloured. As a result the material becomes disfigured. It consequently depreciates in value and may even prove unsaleable. Whilst the effect just referred to is common to various classes of dyestufl', it is particularly prevalent in respect of anthraquinone dyestufls. Especially is this the case with those yielding violet, blue or green shades. By way of example we men.- tion the dyestufis l-amino-4-methylaminoanthraquinone (violet shade), 1:425:8-tetraaminoanthraquinone (blue shade) and 1(p-aminoanilino) 4-acetylmethylaminoanthraquinone (green shade): We have now found that this effect occasioned by the action of fumes from burning coal gas can be advantageously hindered or prevented by applying to the materials consisting of or containing cellulose esters or ethers an N substituted diamine as defined below.

Accordingly the present invention relates to a process for treating materials consisting of or containing cellulose esters or ethers comprising applying thereto an N-substituted diamine of the general formula RR'N-(CHz) n-NRR, wherein R. represents hydrogen, methyl, ethyl or hydroxyethyl; R represents phenyl which may carry simple substituents such as alkoxy, alkyl or halogen, and n stands for 2-6.

By way of N-substituted diamines there may with fumes from burning coal gas. For exmethlyene diamine (respecting. the preparation 1 of the foregoing compounds, see Friihlich, Berichte der. deutschen 'Chemischen Gesellschaft, 1907, 40, 762);,N:N'-diphenylethylene diamine (see Morley, ibid, 1879, 12, 1794), N':N-diphenyl- N:N'-di(B-hydroxyethyl) ethylene diamine (obtainable by condensing N-p-hydroxyethylaniline with ethylene dibromide in the presence of sodium carbonate), NzN' diphenylhexamethylene diamine (prepared by condensing hexamethylene dibromide with aniline in presence of sodium carbonate). A mixture of N-substituted diamines obtained by condensing o-toluidine and aniline with ethylene dichloride in the presence of sodium carbonate, may also be used.

The N-substituted diamines of the present in-.- vention may be appl ed to the above mentioned materials, e. g., cellulose acetate artificial silk,

in any convenient manner. The application of the N-substituted diamines may occur before,

during or after the colouration of the material in question. For example, cellulose acetate artiflcial silk which has already been dyed, may be padded in an alcoholic solution of the desired N-substituted diamine, e. g., N:N-diphenylbe used according to the present invention, for

example, N:N'-dimethyl-N:N'-diphenylethylene diamine, NzN' diethyl N:N'-diphenylethylene diamine, N:N'- dimethyl-N:N'- diphenyltrimethylene diamine, N:N'-diethyl-N:N'-diphenyltriethylene diamine. The cellulose acetate artificial silk is then squeezed to remove the superfluous alcoholic solution, and dried. The N,:N'-

diphenylethylene diamine may also be applied to the cellulose acetate artificial silk in similar manner before the cellulose acetate artificial silk' has been dyed. In place of alcohol other organic solvents can be used to dissolve the. N-

For instance, a strong aqueous dispersion or N:N'-diphenylethylene diamine may be prepared by milling 20 parts thereof in 74 parts of, water with 6 parts of dlsodium dinaphthylmethane disulphonate for 24 hours.

sired, to the actual dyebath in which the cellulose acetate artificial silk is to be dyed. In this manner the N:N'-diphenylethylene diamine is applied to the cellulose acetate artificial silk at the same time as it is dyed. In place of the strong aqueous dispersion of N:N'-diphenylethylene diamine just mentioned, a solution thereof in ethylene '65 glycol monoethyl ether containing as dispersing ENT omen-g This dispersion can then be diluted by adding a little thereof, if de-- 1 material by gas fumes.

1 lug.

late over the fabrics.

- example, be used, are the condensation products from ethylene oxide (30 mols.) and cetyl alcohol (1 mol.), polyglyceryl ricinoleate, cetyl trimethylammonium bromide and sodium cetyl sulphate. Other organic solvents for the N-substituted diamines are, for instance, butyl alcohol and dioxan. The N-substituted diamines may also be brought into aqueous solution for application to the material which it is desired to treat, by dissolving them in the form of their salts, e. g., N:N'-diphenylethylene diamine hydrochloride. It is in that case, however, necessary to liberate the base, i. e., the diamine, by after-treatment with an alkali, e. g., sodium hydroxide, This is because the salts themselves are not effective in hindering or preventing the fading of the Instead of using sodium hydroxide; the material carrying the N-substi- 1 tuted diamine hydrochloride may be soapcd' after which it is found to have been given good protection against the effect of gas fumes.

applied. They have also, as already indicated above, the further advantage that they can be conveniently applied to cellulose acetate artificial silk at the same time as it is dyed. Moreover the present diamines are not toxic.

They are also non-volatile and consequently do not tend to evaporate from the material to which they have been applied. Thus, for example, cellulose acetate artificial silk which has been treated with N :N'-dimethyl-N:N'-diphenylethylene diamine I retains it resistance to the effect of gas fumes which has been conferred by the latter compound, indefinitely, when it is kept in storage.

Although the fading of cellulose acetate artifi- 3 cial silk in the presence of gas fumes may occur somewhat slowly in practice, this effect can be hastened for the purpose of testing the efficiency of compounds designed to inhibit fading, by suspending two patterns of cellulose acetate artificial silk fabric, one treated with the compound it 1 is wished to examine, one untreated, side by side 1 inside a metal chamber connected with, a chimney leading from a Bunsen burner, baille plates being arranged in the metal chamber so as to cause the fumes from the burning gas to circu- In this manner an effect can be produced in two or three hours which I might take as many weeks to reach in, for example, the atmosphere of a warehouse, where gas fumes were present.

The following examples in which the parts are 1 by weight, illustrate, without limiting, the present invention.

Example 1 100 parts of cellulose acetate artificial silk which has been dyed with 1 of 1:4:5z8-tetrasilk is then squeezed so that it retains its own weight of alcoholic solution. After drying, the so-treated material is found to have a much improved resistance to the fumes of burnt gas when compared with the untreated dyed material. This comparison is conveniently carried out by using the fumes from a Bunsen burner in the apparatus already referred to. When tested in this manner the untreated material exhibits very noticeable fading in the course of 3 hours, whereas the material which has been treated with N:N'-diphenylethylene diamine is only slightly affected.

Instead of N:N'-diphenylethylene diamine, N:N'-dimethyl-N:N-diphenylethylene diamine can be employed with similar good results.

Example 2 20 parts of N:N'-diphenylethylene diamine are ball-milled in 74 parts of water with 6 parts of disodium dinaphthylmethane disulphonate for 24 hour. 5 parts of the resulting aqueous dispersion are added together with 1 part of 1:4:5z8-tetraaminoanthraquinone and 9 parts of 50% Turkey red oil to-3000 parts of water. In the dyebath so constituted 100 parts of cellulose acetate artificial silk are dyed at C. for 45 minutes. The material is then taken from the dyebath, rinsed well with water and dried. It is found to possess greatly improved fastness to burnt gas fumes when compared with cellulose acetate artificial silk which has been dyed in the same manner without the addition of the N:N'-diphenylethylene diamine.

Example 3 N:N-diphenylethylene diamine is applied to cellulose acetate artificial silk whilst it is being dyed with 1:4:5:8-tetra-aminoanthraquinone as described in Example 2, except that the N:N'- diphenylethylene diamine is added to the dyebath in the form of a solution instead of an aqueous dispersion. Thus the dyebath is prepared as follows:

1 part of N:N'-diphenylethylene diamine is heated at 60 C. with 2 parts of the condensation product from ethylene oxide (17 mols.) and cetyl alcohol and 7 parts of ethylene glycol monoethyl ether until a clear yellow solution is obtained. This solution is added together with 1 part of 1:4:5:8-tetra-aminoanthraquinone and 9 parts of 50% Turkey red oil to 3000 parts of water.

Example 4 In place of the N:N'-diphenylethylene diamine used in Example 2, N:N'-dimethyl-N:N'-diphenylethylene diamine is employed, the dyebath being made up as follows:

25 parts of N:N-dimethyl-N:N'-diphenylethylene diamine are warmed with 25 parts of the condensation product from ethylene oxide (17 mols.) and cetyl alcohol, 12.5 parts of the condensation product from ethylene oxide (30 mols.) and cetyl alcohol, and 37.5 parts of ethylene glycol monoethyl ether, 4 parts of the resulting solution are added together with 1 part of 1:4:5:8-tetra-aminoanthraquinone and 9 parts of 50% Turkey red oil to 3000 parts of water.

Example 5 1 part of N:N'-diphenylhexamethylene diamine is heated at 60 C. with 1.5 parts of the condensation product from ethylene oxide (17 mols.) and cetyl alcohol (1 mol.), and 7.5 parts of ethylene glycol monoethyl ether until a clear yellow solution is obtained. 10 parts of this solution are added together with 1 part 1:4:5z8-tetra-aminoanthraquinone and 9 parts of 50% Turkey red oil to 300 parts of water. In the dyebath so prepared 100 parts of cellulose acetate artificial silk are dyed as described in Example 1, The dyed material is much faster to bumtga's fumes than the same material similarly dyed except that no N :N'-diphenylhexamethylene diamine is included in the dyebath.

We claim:

1. The process for improving the resistance to fume fading of colorations on materials comprised of cellulosic compounds from the group consisting of cellulose esters and cellulose ethers which comprises incorporating in said materials N:N'-diphenylethylene diamine.

2. The process for improving the resistance to fume fading of colorations on cellulose acetate materials which comprises incorporating in said materials N:N'-diphenylethylene diamine.

3. Dyed materials resistant to fume fading and comprised of cellulosic compounds from the groupflwnw consisting of cellulose esters and'ce'lliilose ethers, and having incorporated therein N:N'-diphenylethylene diamine.

4. Dyed materials resistant to fume fading and comprised of cellulose acetate, and having incorporated therein N :N'-diphenylethylene -di-' amine.

BENJAMIN COLLIE. CHARLES HUGHYGILES. DONALD GRAHAM WILKINSON.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Name Date Ellis Oct. 10, 1933 Ellis May 8, 1934 McNally Oct. 13. 1942 Number 

